Extreme Diels-Alder Reactions Your Chemistry Teacher Warned You About

[@totalsynthesis]

💘 Big thanks again to all channel supporters and followers! Let me know any feedback and recommendations for future videos. www.patreon.com/totalsynthesis; instagram.com/totalsynthesis_official/ Regarding pedrolide, I've just realized Synthesis Workshop has a video kzbin.info/www/bejne/raqYenl8arprmZo that you should check out for direct commentary of the lead chemist, including in-depth information (e.g., optimization studies).

[@chemicalboy2106]

Man I'm still absolutely mesmerized by the Petrolide synthesis by Marlene Fadel and Carreira, I am fortunate enough to take a course by Prof. Carreira and Ms. Fadel was my Lab TA, which is quite surreal honestly!

[@totalsynthesis]

The time between first isolation and completed synthesis, particularly considering the structural complexity, is pretty insane!

[@chemicalboy2106]

@@totalsynthesis Absolutely, I was talking to Carreira and he was really proud of their timely achievement. Are you also around at ETH?

[@trimethylsilyltrifluoromet2099]

Wow that cyclopentadiene unmasking was one of the most beautiful reactions I have ever seen. Thanks for the video.

[@totalsynthesis]

That was straight up 🔥 Thanks!

[@SharpAssKnittingNeedles]

I love that this is all way over my head (undergrad and only been up through ochem1) watching your vids on crazy shit like this stokes my thirst to understand every minute detail you're talking about even though I can generally follow along. Thank you and wish I was in a position to be a patron ❤

[@totalsynthesis]

Thanks a lot!

[@theWinterWalker]

I love spotting neurodivergent folks that genuinely get excited about knowledge and thirst to learn 👌🏻

[@yxlop4893]

Amazing videos, Im mostly overwhelmed by the end, but thats how it should be.

[@totalsynthesis]

Thanks!

[@derenjoy3r]

This is the good shit. Nice vid

[@totalsynthesis]

Thanks mate

[@C4pungMaster]

Phytochemistry alkaloid chem fan vs Marine chemistry enjoyer. Both known for decimating half the population of a species trying to isolate a single active compound that have utterly deranged scaffolds 😂

[@totalsynthesis]

😂😂

[@eoinpasquetti4114]

You included the wrong reference for the eel paper. Though the one you cited also deals with massacring eels. "J. Am. Chem. Soc. 1990, 112, 11, 4380-4386" is the one you quote from in the video.

[@totalsynthesis]

Oh snap, thanks! I mixed up my massacres

[@AlphaNumeric123]

At 9:53 you mention that they use Bu4NBr as a phase transfer catalyst for CsF. Why not just use TBAF (Bu4NF) instead? I think I'm missing something obvious, but I'm confused! Great work, keep it up! I much prefer the serious takes with only a few jokes, so I really like this video. You're awesome!

[@totalsynthesis]

Thanks! Not sure if they document it anywhere but maybe that system simply proved experimentally to be superior

[@AlphaNumeric123]

@@totalsynthesis thanks! I reply if I find anything. Again, really great work. Thank you so much for creating high-quality synthesis content that is both entertaining and educational

[@AlphaNumeric123]

@@totalsynthesis Now that I think of it, I wonder if using TBABr and CsF instead of TBAF alone was chosen because this allows you to control two variables--the stoichiometry of fluoride and the amount of phase transfer catalyst. The only other thing I can think of is the resulting salt formation/counterion size might in some way be related

[@totalsynthesis]

@@AlphaNumeric123 Good points!

[@TenkArizona]

In general, CsF is poorly soluble in ACN so the F is slowly released allowing the hugely reactive Allene to remain in low concentrations throughout the reaction. When TBAF is used, even under slow addition w a syringe pump, the Allene is generated too quickly and can lead to dimerization via 2+2 or other unwanted reactivity. This is true of benzyne formation as well. This is a funny case where the CsF need a little help at colder temperature so it acts as a way to increase available F while not flooding the reaction w F. Hope this helps 😊

[@brettmoore3194]

I thought I was ready but maybe a few more months of digesting data🎉

[@glebanful]

I would have synthesized those compouds much earlier, but there was an easier way to get a Nobel prize🎉

[@totalsynthesis]

Your Diels Alder mechanism proposed in 1942 proved to be a bit sus though: pubs.acs.org/doi/10.1021/ja01264a521

[@MandrakeFernflower]

Pufferfish and friends

[@microwavesynth4659]

omg I found my brother